EP4232434A1 - Heical dispirodiindenopyridines and dispirodiindenopyridazines, and preparation and uses thereof - Google Patents
Heical dispirodiindenopyridines and dispirodiindenopyridazines, and preparation and uses thereofInfo
- Publication number
- EP4232434A1 EP4232434A1 EP20855888.2A EP20855888A EP4232434A1 EP 4232434 A1 EP4232434 A1 EP 4232434A1 EP 20855888 A EP20855888 A EP 20855888A EP 4232434 A1 EP4232434 A1 EP 4232434A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- preparation
- summary diagram
- formula
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000010586 diagram Methods 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- -1 for example Chemical group 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- IGVKWAAPMVVTFX-BUHFOSPRSA-N (e)-octadec-5-en-7,9-diynoic acid Chemical compound CCCCCCCCC#CC#C\C=C\CCCC(O)=O IGVKWAAPMVVTFX-BUHFOSPRSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- KAFZOLYKKCWUBI-HPMAGDRPSA-N (2s)-2-[[(2s)-2-[[(2s)-1-[(2s)-3-amino-2-[[(2s)-2-[[(2s)-2-(3-cyclohexylpropanoylamino)-4-methylpentanoyl]amino]-5-methylhexanoyl]amino]propanoyl]pyrrolidine-2-carbonyl]amino]-5-(diaminomethylideneamino)pentanoyl]amino]butanediamide Chemical compound N([C@@H](CC(C)C)C(=O)N[C@@H](CCC(C)C)C(=O)N[C@@H](CN)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CC(N)=O)C(N)=O)C(=O)CCC1CCCCC1 KAFZOLYKKCWUBI-HPMAGDRPSA-N 0.000 claims description 3
- HPKJGHVHQWJOOT-ZJOUEHCJSA-N N-[(2S)-3-cyclohexyl-1-oxo-1-({(2S)-1-oxo-3-[(3S)-2-oxopyrrolidin-3-yl]propan-2-yl}amino)propan-2-yl]-1H-indole-2-carboxamide Chemical compound C1C(CCCC1)C[C@H](NC(=O)C=1NC2=CC=CC=C2C=1)C(=O)N[C@@H](C[C@H]1C(=O)NCC1)C=O HPKJGHVHQWJOOT-ZJOUEHCJSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- SHAHPWSYJFYMRX-GDLCADMTSA-N (2S)-2-(4-{[(1R,2S)-2-hydroxycyclopentyl]methyl}phenyl)propanoic acid Chemical compound C1=CC([C@@H](C(O)=O)C)=CC=C1C[C@@H]1[C@@H](O)CCC1 SHAHPWSYJFYMRX-GDLCADMTSA-N 0.000 claims 1
- TZKBVRDEOITLRB-UHFFFAOYSA-N 4-methyl-n-[4-[(4-methylpiperazin-1-yl)methyl]-3-(trifluoromethyl)phenyl]-3-[2-(1h-pyrazolo[3,4-b]pyridin-5-yl)ethynyl]benzamide Chemical compound C1CN(C)CCN1CC(C(=C1)C(F)(F)F)=CC=C1NC(=O)C1=CC=C(C)C(C#CC=2C=C3C=NNC3=NC=2)=C1 TZKBVRDEOITLRB-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 239000003153 chemical reaction reagent Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 30
- 239000000741 silica gel Substances 0.000 description 28
- 229910002027 silica gel Inorganic materials 0.000 description 28
- 239000011541 reaction mixture Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000011160 research Methods 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000004587 chromatography analysis Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 10
- 239000012467 final product Substances 0.000 description 10
- 239000000543 intermediate Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000010511 deprotection reaction Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 7
- 150000001345 alkine derivatives Chemical class 0.000 description 7
- 238000003818 flash chromatography Methods 0.000 description 7
- 239000013067 intermediate product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- YDYNSAUGVGAOLO-UHFFFAOYSA-N 2,6-dibromobenzaldehyde Chemical compound BrC1=CC=CC(Br)=C1C=O YDYNSAUGVGAOLO-UHFFFAOYSA-N 0.000 description 4
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005905 alkynylation reaction Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000005441 aurora Substances 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 125000003003 spiro group Chemical group 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000001502 aryl halides Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 2
- IJSCYVYSFUUQBN-UHFFFAOYSA-N 2-[2-(2-formylphenyl)ethynyl]benzaldehyde Chemical compound O=CC1=CC=CC=C1C#CC1=CC=CC=C1C=O IJSCYVYSFUUQBN-UHFFFAOYSA-N 0.000 description 2
- ZEDSAJWVTKUHHK-UHFFFAOYSA-N 2-ethynylbenzaldehyde Chemical compound O=CC1=CC=CC=C1C#C ZEDSAJWVTKUHHK-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910013458 LiC6 Inorganic materials 0.000 description 2
- 150000001204 N-oxides Chemical class 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 239000007819 coupling partner Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000006464 oxidative addition reaction Methods 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006894 reductive elimination reaction Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003413 spiro compounds Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006478 transmetalation reaction Methods 0.000 description 2
- 239000011995 wilkinson's catalyst Substances 0.000 description 2
- UTODFRQBVUVYOB-UHFFFAOYSA-P wilkinson's catalyst Chemical compound [Cl-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Rh+](P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTODFRQBVUVYOB-UHFFFAOYSA-P 0.000 description 2
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- QVANIYYVZZLQJP-UHFFFAOYSA-N 1-benzothiophen-3-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CSC2=C1 QVANIYYVZZLQJP-UHFFFAOYSA-N 0.000 description 1
- CYGUXEZVBLMVRV-UHFFFAOYSA-N 1-bromonaphthalene-2-carbaldehyde Chemical compound C1=CC=C2C(Br)=C(C=O)C=CC2=C1 CYGUXEZVBLMVRV-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- GEICDMWIZIQEEI-UHFFFAOYSA-N 2,3-dibromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1Br GEICDMWIZIQEEI-UHFFFAOYSA-N 0.000 description 1
- CUKSTNNYAHZPRM-UHFFFAOYSA-N 2-bromo-4-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=C(C=O)C(Br)=C1 CUKSTNNYAHZPRM-UHFFFAOYSA-N 0.000 description 1
- ODISAUHBLBVQKC-UHFFFAOYSA-N 2-bromo-4-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(Br)=C1 ODISAUHBLBVQKC-UHFFFAOYSA-N 0.000 description 1
- VGOIJJANJVWLQO-UHFFFAOYSA-N 2-bromo-6-methylbenzaldehyde Chemical compound CC1=CC=CC(Br)=C1C=O VGOIJJANJVWLQO-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 101100328886 Caenorhabditis elegans col-2 gene Proteins 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000006006 cyclotrimerization reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002519 electronic circular dichroism spectroscopy Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/20—Spiro-condensed ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/36—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Definitions
- the present invention concerns dispiroindenopyridines and/or dispiroindenopyridazines and derivatives thereof, methods for their preparation, the study and definition of their properties, and their uses.
- the present invention relates to the preparation of new classes of helical molecules represented by the following general formulae A) and/or A') and/or B) and/or B') for use in applications in the field of organic electronics, since they have proved to have greater and more advantageous properties in comparison with the other organic molecules that may be taken into consideration as candidates for the same use.
- A), A') and B), B') represent, respectively, derivatives of heical dispiroindenopyridines and dispiroindenopyridazines , as will be described in detail in the following description .
- inorganic electronics is essentially based on materials characterized by good electron mobility due to the presence of ionic or covalent bonds in their crystalline structure; however, it still has a number of drawbacks such as, for example, the need for complex equipment, high costs, and lack of mechanical flexibility .
- Organic-based electronics is expected to shortly replace inorganic electronics because of its numerous potential advantages in terms of, for example, flexibility, low cost, easy material deposition, possibility of production in environmentally-friendly conditions, appropriate modulation of the electronic properties by chemical synthesis, and so forth. Nevertheless, the current research has not yet provided a competitive practical solution that could be used as an alternative to those currently known and implemented in the art.
- the present invention concerns two novel classes of molecules represented by, respectively, the following general formulae A) and/or A') and/or B) and/or B'): wherein A), A'), B), B') represent each, respectively, derivatives of helical dispiroindenopyridines [A) and A')] and dispiroindenopyridazines [B) and B')]; and wherein R and R' independently represent hydrogen, an optionally substituted C 1 -C 6 hydrocarbon group (wherein the substituents may be straight-chain or, preferably, branched-chain ones in order to further stiffen the molecular structure and promote fluorescence), an optionally substituted aromatic group (e.g.
- phenyl benzyl, p-tolyl, 4-methoxyphenyl, 4-bromophenyl, (trifluoromethyl)benzyl, thiophen-3-yl, naphthalen-1- yl, o-tolyl), or a trimethylsilyl group;
- the X's represent each, independently, an optionally substituted C 1 -C 6 hydrocarbon group (wherein the substituents may be straight-chain or, preferably, branched-chain ones in order to further stiffen the molecular structure and promote fluorescence), a trifluoromethyl group, a difluoromethyl group, a phenyl group, a benzyl group, or an alcoxyl group.
- Said cocyclotrimerization reaction was found to be particularly preferable because of its peculiar advantageous properties, such as, for example, high atomic economy, mild reaction conditions, triple-bond selective catalysts, tolerance for different functional groups, regioselectivity in intramolecular reactions.
- Experimental procedures for effecting this cocyclotrimerization reaction apply a general method for the cyclotrimerization of the compounds 5a and 5b of Summary Diagram 1 and 10a and 10b of Summary Diagram 2_, respectively, in the presence of a metallic catalyst M based on complexes of Rh and/or Co and/or Ni and/or Ir.
- said catalyst M may be selected among the group including known complexes of rhodium (e.g. Wilkinson's catalyst
- Procedure 1 A dry microwave vial is loaded with the starting material, which is dissolved in a solvent like, for example, tetrahydrofuran (THE) under argon atmosphere. After the addition of a catalyst, e.g. the above-mentioned Wilkinson's catalyst, and of additional Ag 2 CO 3 , the reaction vessel is sealed and heated in a microwave reactor. The reaction mixture is then cooled to room temperature and the solvent is evaporated under reduced pressure to give the raw final product.
- a solvent like, for example, tetrahydrofuran (THE) under argon atmosphere.
- Procedure 2 A catalyst like, for example, cyclopentadienyl cobalt dicarbonyl, is added as a single portion to a solution of the starting compound in a solvent like, for example, p-xylene, in a carousel tube.
- the reaction vessel is heated in a carousel under argon atmosphere. If the reaction is slow, an additional quantity of catalyst is added during the reaction until the starting material is consumed.
- the mixture is diluted with dichloromethane (CH 2 CI 2 ), filtered through a thin layer of silica gel, and concentrated under a vacuum. The subsequent purification of the residue by flash chromatography on silica gel gives the desired cyclized product .
- Procedure 3 A catalyst like, for example, cyclopentadienyl cobalt dicarbonyl, is added as a single portion to a solution of the starting product in a solvent like, for example, THF, under argon atmosphere.
- the reaction mixture is pumped through a flow reactor under high pressure and at high temperature.
- the resulting mixture is then filtered and concentrated under a vacuum.
- the subsequent purification of the residue by flash chromatography on silica gel gives the desired cyclized product.
- Procedure 4 A round-bottom side-arm flask containing Col2(dppe) and Zn is emptied and purged with nitrogen gas.
- the starting product and a solvent like, for example, acetonitrile (CH3CN) are then added into the flask by means of syringes.
- the reaction is then stirred.
- the mixture is diluted with CH 2 CI 2 and filtered through celite and silica gel, and then the filtrate is concentrated.
- the raw residue is then purified through a column of silica gel to give the pure final product.
- reaction mixture is then treated with methyl iodide and stirred for 25 minutes at -78°C.
- the reaction mixture is then left to heat to room temperature for about 1.5 hours.
- the resulting solution is quenched with HCl and stirred at room temperature for 1.5 hours.
- reaction mixture is subsequently extracted with Et 2 O, the united organic layers are washed with a solution of 10% aqueous sodium thiosulfate and water, dried on MgSO 4 , filtered and evaporated under a vacuum.
- the resulting yellowish solid is purified by distillation in a Kugelrohr apparatus to give the final product as white crystals.
- the modes of operation and the reagent quantities employed were inferred and gathered from: Krzeszewski, M; et al., Chemistry-A European Journal 2016, 22(46), 16478, which is therefore incorporated herein by reference in its entirety.
- a toluene/water mixture (1:1, v:v) is added into the flask, and the resulting mixture is stirred at 80°C for 16 hours. After cooling, the two phases are separated and the aqueous phase is extracted with ethyl acetate. The organic phases are combined and the solvent is evaporated. The raw product thus obtained is then purified by flash chromatography through silica gel.
- Dibromobenzaldehyde, benzo [b]thien-3-yl-boronic acid, K 2 CO 3 , PPh 3 and Pd(OAc) 2 are introduced into a Schlenk flask, and all is purged with argon before use.
- a mixture of toluene/water (1:1, v:v) is added into the flask, and the resulting mixture is stirred for 16 hours at 80°C. After cooling, the two phases are separated and the aqueous phase is extracted with ethyl acetate. Then the organic phases are combined and dried, and the solvent is evaporated.
- the raw product thus obtained is purified by flash chromatography through silica gel.
- the starting compound, CuI and Et 3 N are added to a mixture of dichlorobis (triphenylphosphine)palladium and aryl halide in THE.
- the resulting mixture is stirred at 50°C overnight, then the reaction mixture is diluted with a saturated aqueous solution of NH 4 CI.
- the resulting mixture is extracted three times with ethyl acetate, then the organic extracts are combined, washed with brine and dried on Na2SO4. The mixture is filtered and evaporated under reduced pressure. Finally, the residue is purified by chromatography through silica gel to give the above final product 3.
- Trimethylsilylacetylene, CuI and Et 3 N are added to a mixture of dichlorobis (triphenylphosphine)palladium and aryl halide in THE.
- the resulting mixture is kept under agitation at 50°C overnight, then the reaction mixture is diluted with a saturated aqueous solution of NH 4 CI.
- the resulting mixture is extracted three times with ethyl acetate, then the organic extracts are combined, washed with brine and dried on Na2SO4. The mixture is filtered and evaporated under reduced pressure. Finally, the residue is purified by chromatography through silica gel to give the product.
- K 2 CO 3 is added to acetylene protected with trimethylsilyl.
- the mixture is diluted with water and then extracted three times with CH 2 CI 2 .
- the organic layers are then united, washed with brine and dried on Na2SO4.
- the mixture is filtered and evaporated under reduced pressure, and the residue is purified by chromatography through a column of silica gel to give the product.
- the latter, CuI and Et 3 N are added to a mixture of dichlorobis (triphenylphosphine)palladium and aryl halide in THF.
- the resulting mixture is kept under agitation at 50°C overnight, then the reaction mixture is diluted with a saturated aqueous solution of NH 4 CI.
- This type of reaction is a reaction of addition of 2 moles of cyanide ion, hydrogen cyanide or alkylsilyl cyanide (with subsequent deprotection) to the aldehyde.
- the reaction is novel, but the reaction type is classical and generally feasible.
- the intermediate product 5b cyanohydrin or cyanohydrin silyl ether
- the intermediate product 5b is not known in the literature; therefore, it is a part of the present invention.
- PCC Precipitated Calcium Carbonate
- celite is added to a solution of the diol in anhydrous CH 2 CI 2 under argon atmosphere, and the resulting mixture is stirred for 3 hours at 25°C. Subsequently, the reaction mixture is filtered through a layer of silica gel/celite, washed with CH 2 CI 2 and concentrated under reduced pressure. A chromatography through a column of silica gel gives the desired oxidized product.
- reaction mixture is subsequently diluted with water and neutralized with a saturated solution of K 2 CO 3 , then extracted with Et 2 O.
- organic fractions are united, dried on MgSO 4 , filtered and concentrated under reduced pressure.
- a chromatography through a column of silica gel gives the desired final product B).
- Example 13 To the inventor's knowledge, the intermediate product 4 is not known in the scientific literature; therefore, it is also a part of the invention.
- n-BuLi is added dropwise to a solution of alkyne in anhydrous THE at -78°C. After stirring, the starting compound in THE is added and the reaction mixture is first stirred at -78°C and then allowed to heat to room temperature, still under agitation. Subsequently, an aqueous solution of NH 4 CI is used in order to quench the reaction mixture, which is then extracted with Et 2 O. The organic fractions are united, washed with a saturated solution of NaCl, separated and dried on Na2SO4, filtered and concentrated under reduced pressure. A chromatography through a column of silica gel of the obtained residue gives the desired product 4.
- Example 14 To the inventor's knowledge, the starting compound 4 and the intermediate 5a are not known in the scientific literature; therefore, they are also a part of the invention.
- this type of reaction is a reaction of addition of a cyanide ion, hydrogen cyanide or alkylsilyl cyanide (with subsequent deprotection) to the aldehyde.
- a particularly preferred one for the purposes of the present invention turned out to be Kaiser, Reinhard P.; et al., Angew. Chem. Int. Ed. 2019, 58, 17169.
- the modes of operation and the reagent quantities employed for this reaction were, in fact, inferred and gathered from the same publication, which is therefore incorporated herein by reference in its entirety.
- This reaction is a reaction of nucleophilic addition of 2 moles of cyanide ions, hydrogen cyanide or alkyl silyl cyanide (with subsequent deprotection) which is similar to those previously described herein, and is therefore carried out, for example, in the same conditions and with substantially the same quantities as in the similar reaction previously described in Example 10.
- n-BuLi is added dropwise to a solution of alkyne in anhydrous THE at -78°C, and the reaction is first stirred at -78°C and then left to heat to room temperature, still under agitation. The reaction mixture is then quenched by adding an aqueous solution of NH 4 CI and extracted with Et 2 O, and the organic phases are united, washed with a saturated solution of NaCl, dried on anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue thus obtained is purified by chromatography through a column of silica gel to give the above intermediate product 9.
- This reaction is a reaction of nucleophilic addition of a cyanide ion, hydrogen cyanide or alkylsilyl cyanide (with subsequent deprotection) to the aldehyde which is similar to the one previously described herein, and is therefore carried out, for example, in the same conditions and with substantially the same quantities as in the similar reaction described in Example 14.
- Example 21 To the inventor's knowledge, the starting compound 11a and the oxidized intermediate product are not known in the scientific literature; therefore, they are also a part of the invention.
- the Suzuki reaction is a cross-coupling reaction where the coupling partners are a boronic acid and an organohalide catalyzed by a Pd(0) complex. It was first published in 1979 by Akira Suzuki (Miyaura, N.; Yamada, K.; Suzuki, A.; et al.; Tetrahedron Lett. 1979, 36, 3437).
- a carbon-carbon single bond is formed by coupling an organoboron species with a halide using a palladium catalyst and a base.
- novel heical molecules of dispirodiindenopyridines and dispirodiindenopyridazines of the present invention have proved to have greater and better characteristics for organic electronics applications, in comparison with the other known molecules that may be taken into consideration as candidates for the same use.
- Said characteristics can be attributed, in particular, to the presence of: 1) largely conjugated systems, 2) chiro-optical properties due to helicity, 3) spiro residues (which confer increased morphologic stability, while at the same time maintaining the electronic properties and having higher solubility than the corresponding compounds without spiro groups), 4) increased fluorescence due to the presence of the pyridazine residue and to the rigid structure of the spiro residue, and 5) functionalization due to the presence of nitrogen atoms (which may lead to formation of a so-called "push-pull" system, modulability through formation of pyridinium and pyridazinium salts, formation of N-oxides or N,N'-dioxides as anchoring groups for solar cells, and so forth).
- dispirodiindenopyridazines seem to be the only existing class of molecules which possess two fluorophores groups (fluorene and pyridazine); thus, they permit a better modulation of optoelectronic properties such as, for example, multicolor fluorescence, and may originate new uses for making special materials such as, for example, smart luminescent materials.
- dispirodiindenopyridines and dispirodiindenopyridazines Being spiro compounds, dispirodiindenopyridines and dispirodiindenopyridazines are characterized by steric factors that prevent solid-state packing; as a consequence, they have proved to be capable of reducing intermolecular interaction, thereby preserving the color purity and spectral stability of the fluorescence.
- chiro-optical properties of the helical dispirodiindenopyridines and dispirodiindenopyridazines are important in organic electronics, e.g. for the electronic circular dichroism or for use in chiral sensors. In fact, chirality is an additional property which is advantageous for organic electronics.
- the protonation of the nitrogen atom may originate multicolor fluorescence because of the emission variation; this is essential for a smart luminescent material.
- the presence of the nitrogen atom permits the functionalization and formation of a system characterized by the presence of a donor and an acceptor of electrons; all this is fundamental for the polarization of a "push-pull" system.
- N-oxide turned out to be essential to confer the organic sensitizer property on the anchoring in a solar cell in order to increase absorption, i.e. to attain higher energy conversion efficiency.
- Crystalline silicon offers many advantages, such as abundance, a radicated basic technology, the fact that it is a high-quality, high-stability material. Nevertheless, the most important drawbacks connected with silicon use are its indirect energy gap and the high costs incurred for fabricating silicon-based materials and devices.
- organic cells have the advantage that they can have different hues.
- the derivative compounds of dispirodiindenopyridines and dispirodiindenopyridazines of the present invention have thus proven to be particularly promising and useful for use in the organic electronics field.
- the present invention has made it possible to realize novel derivative heical molecules of dispirodiindenopyridines and dispirodiindenopyridazines , and derivatives thereof, which have proven to be particularly useful in organic electronics applications, in comparison with both the inorganic compounds currently in use and the other organic molecules currently being taken into account as possible competitive candidates for such applications.
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Abstract
The present invention concerns dispiroindenopyridines and dispiroindenopyridazines and derivatives thereof, methods for their preparation, the study and definition of their properties, and their uses. In particular, the present invention relates to the preparation of new classes of heical molecules represented by the general formulae A) and/or A') and/or B) and/or B') for use in applications in the field of organic electronics, since they have proved to have greater and more advantageous properties in comparison with the other known organic molecules that may be taken into consideration as candidates for the same use.
Description
Title:
"HELICAL DISPIRODIINDENOPYRIDINES AND
DISPIRODIINDENOPYRIDAZINES, AND PREPARATION AND USES
THEREOF"
DESCRIPTION
Technical Field of the Invention
The present invention concerns dispiroindenopyridines and/or dispiroindenopyridazines and derivatives thereof, methods for their preparation, the study and definition of their properties, and their uses. In particular, the present invention relates to the preparation of new classes of helical molecules represented by the following general formulae A) and/or A') and/or B) and/or B') for use in applications in the field of organic electronics, since they have proved to have greater and more advantageous properties in comparison with the other organic molecules that may be taken into consideration as candidates for the same use.
In said formulae, A), A') and B), B') represent,
respectively, derivatives of heical dispiroindenopyridines and dispiroindenopyridazines , as will be described in detail in the following description .
Description of the Prior Art
Drawbacks and/or Problems
At present, inorganic electronics is essentially based on materials characterized by good electron mobility due to the presence of ionic or covalent bonds in their crystalline structure; however, it still has a number of drawbacks such as, for example, the need for complex equipment, high costs, and lack of mechanical flexibility .
Organic-based electronics is expected to shortly replace inorganic electronics because of its numerous potential advantages in terms of, for example, flexibility, low cost, easy material deposition, possibility of production in environmentally-friendly conditions, appropriate modulation of the electronic properties by chemical synthesis, and so forth. Nevertheless, the current research has not yet provided a competitive practical solution that could be used as an alternative to those currently known and implemented in the art.
Technical Problem
Therefore, the need is still felt in the art for novel organic compounds having the above-mentioned favourable characteristics, so as to fulfil a greater number of requirements than the other known molecules for applications in the electronics field in general, and particularly in the organic electronics field.
Summary of the invention
While tackling the above-described problem, the present
inventor conducted an in-depth study on the correlation between the structure and the properties of organic molecules that may potentially be used in the field of organic electronics. As a result of said study, the inventor found that two novel classes of helical dispiroindenopyridines and/or, respectively, dispiroindenopyridazines, and their derivatives, could provide an adequate solution to the above-mentioned technical problem. It is therefore one object of the present invention to provide two classes of molecules (helical dispiroindenopyridines and/or dispiroindenopyridazines, and derivatives thereof) represented by the general formulae A) and/or A') and/or B) and/or B'), respectively, as set out in the following description and in the appended independent claim.
It is another object of the present invention to provide a method for the preparation of said molecules, as set out in the following description and in the appended independent claim.
It is a further object of the present invention to provide the use of said molecules in the field of organic electronics, as set out in the following description and in the appended independent claim. It is yet another object of the present invention to provide novel intermediates for the preparation of said molecules, as set out in the following description and in the corresponding claims appended hereto. Further aspects of the present invention are set out in the appended dependent claims.
Detailed Description of the Invention The present invention concerns two novel classes of molecules represented by, respectively, the following
general formulae A) and/or A') and/or B) and/or B'): wherein A), A'), B), B') represent each, respectively, derivatives of helical dispiroindenopyridines [A) and A')] and dispiroindenopyridazines [B) and B')]; and wherein R and R' independently represent hydrogen, an optionally substituted C1-C6 hydrocarbon group (wherein the substituents may be straight-chain or, preferably, branched-chain ones in order to further stiffen the molecular structure and promote fluorescence), an optionally substituted aromatic group (e.g. phenyl, benzyl, p-tolyl, 4-methoxyphenyl, 4-bromophenyl, (trifluoromethyl)benzyl, thiophen-3-yl, naphthalen-1- yl, o-tolyl), or a trimethylsilyl group;
The X's represent each, independently, an optionally substituted C1-C6 hydrocarbon group (wherein the substituents may be straight-chain or, preferably, branched-chain ones in order to further stiffen the molecular structure and promote fluorescence), a trifluoromethyl group, a difluoromethyl group, a phenyl
group, a benzyl group, or an alcoxyl group.
Preferred methods according to the present invention for the preparation of the compounds of general formulae A) and B) and, respectively, A') and B') are summarized below by way of example in the following summary diagrams Summary Diagram 1 and Summary Diagram 2,,which also fall within the scope of the invention.
Summary Diagram 1
2,6-dibromobenzaldehydeanditsderivativeswithX=-CH3,- CH2-CH3,C6H5-,-OCH3and-OCH2CH3 inposition4or -OCHsand-CH3 inposition3arecommerciallyavailable
2-bromobenzaldehydeanditsderivativeswith X=H andR=C6H5-orX=-OCH3 and-CF3 inposition4andR=H arecommercially available
ThecompoundwithR’=H andX=H is
Sonogashiracoupling commerciallyavailable
Sonogashiracoupling
R’=H orR
(thecorrespondingalkyneis X=H ororganicresidue
commerciallyavailable)
Nucleophilicadditionof2molesof
cyanideion,hydrogencyanideor alkylsilylcyanidewithsubsequent
Alkynylation deprotection
Nucleophilicadditionof1moleofcyanide ion,hydrogencyanideoralkylsilylcyanide Cocyclotrimerization withsubsequentdeprotection
R”=H ororganicresidue
Cocyclotrimerization
1)Oxidation
2)2-LiC6H4-Ph
1)Oxidation
2)2-LiC6H4-Ph
Summary Diagram 2
Commerciallyavailable
Sonogashiracoupling
Nucleophilicadditionof2molesof cyanideion,hydrogencyanideor alkylsilylcyanidewithsubsequent deprotection
Nucleophilicadditionof1moleofcyanide ion,hydrogencyanideoralkylsilylcyanide withsubsequentdeprotection
B')
The key phase of said preparation methods of the present invention is the so-called " Cocyclotrimerization" reaction, which provides the intermediate compounds 6a, 6b (Summary Diagram 1), 11a, lib (Summary Diagram 2), respectively .
Said cocyclotrimerization reaction was found to be particularly preferable because of its peculiar advantageous properties, such as, for example, high atomic economy, mild reaction conditions, triple-bond selective catalysts, tolerance for different functional groups, regioselectivity in intramolecular reactions. Experimental procedures for effecting this cocyclotrimerization reaction apply a general method for the cyclotrimerization of the compounds 5a and 5b of Summary Diagram 1 and 10a and 10b of Summary Diagram 2_, respectively, in the presence of a metallic catalyst M based on complexes of Rh and/or Co and/or Ni and/or Ir.
By way of non-limiting example, said catalyst M may be selected among the group including known complexes of rhodium (e.g. Wilkinson's catalyst
(chlorotris(triphenyl-phosphine)rhodium(I), RhCl(PPh3)3) and the like), cobalt (CpCo(L2) and the like), nickel (Ni(cod)2 + 3PPhs, and the like), iridium (IrCl(cod)2 and the like).
The following will illustrate, by way of non-limiting example, some of the most preferred embodiments of said cocyclotrimerization reaction according to the present invention .
Procedure 1) A dry microwave vial is loaded with the starting material, which is dissolved in a solvent like, for example, tetrahydrofuran (THE) under argon
atmosphere. After the addition of a catalyst, e.g. the above-mentioned Wilkinson's catalyst, and of additional Ag2CO3, the reaction vessel is sealed and heated in a microwave reactor. The reaction mixture is then cooled to room temperature and the solvent is evaporated under reduced pressure to give the raw final product.
The modes of operation and the reagent quantities employed were inferred and gathered from publication: Angew. Chem. Int. Ed. 2019, 58, 17169-17174, which is therefore attached hereto by reference.
Procedure 2) A catalyst like, for example, cyclopentadienyl cobalt dicarbonyl, is added as a single portion to a solution of the starting compound in a solvent like, for example, p-xylene, in a carousel tube. The reaction vessel is heated in a carousel under argon atmosphere. If the reaction is slow, an additional quantity of catalyst is added during the reaction until the starting material is consumed. After cooling to room temperature, the mixture is diluted with dichloromethane (CH2CI2), filtered through a thin layer of silica gel, and concentrated under a vacuum. The subsequent purification of the residue by flash chromatography on silica gel gives the desired cyclized product .
The modes of operation and the reagent quantities employed were inferred and gathered from: Chem. Eur. J. 2014, 20, 8477-8482, which is therefore incorporated herein by reference in its entirety.
Procedure 3) A catalyst like, for example, cyclopentadienyl cobalt dicarbonyl, is added as a single portion to a solution of the starting product in a solvent like, for example, THF, under argon
atmosphere. The reaction mixture is pumped through a flow reactor under high pressure and at high temperature. The resulting mixture is then filtered and concentrated under a vacuum. The subsequent purification of the residue by flash chromatography on silica gel gives the desired cyclized product.
The modes of operation and the reagent quantities employed were inferred and gathered from: Chem. Eur. J. 2014, 20, 8477-8482, which is therefore incorporated herein by reference in its entirety.
Procedure 4) A round-bottom side-arm flask containing Col2(dppe) and Zn is emptied and purged with nitrogen gas. The starting product and a solvent like, for example, acetonitrile (CH3CN) are then added into the flask by means of syringes. The reaction is then stirred. When the reaction is complete, the mixture is diluted with CH2CI2 and filtered through celite and silica gel, and then the filtrate is concentrated. The raw residue is then purified through a column of silica gel to give the pure final product.
The modes of operation and the reagent quantities employed were inferred and gathered from: Org. Lett., Vol.9, No.3, 2007, which is therefore incorporated herein by reference in its entirety.
Procedure 5) The starting product is dissolved in pyridine and acetic anhydride (AC2O) along with several crystals of dimethylaminopyridine (DMAP). The reaction is stirred at room temperature. Finally, the reaction mixture is concentrated under a vacuum to give the raw final product, which is then purified by flash chromatography on silica gel.
The modes of operation and the reagent quantities
employed were inferred and gathered from: Org. Lett., Vol.9, No.3, 2007, which is therefore incorporated herein by reference in its entirety.
Procedure 6) Cyclopentadienyl cobalt dicarbonyl is added as a single portion to a solution of the starting product in p-xylene in a carousel tube. The reaction vessel is heated in a carousel to 140°C under argon atmosphere. If the reaction is slow, more cyclopentadienyl cobalt dicarbonyl is added as 0.5 equivalent portions during the reaction until the starting material is completely consumed. When the reaction is complete, the mixture is cooled to room temperature, diluted with CH2CI2, filtered through a thin layer of silica gel and concentrated under a vacuum. The residue is purified by flash chromatography through silica gel to give the desired purified final product.
The modes of operation and the reagent quantities employed were inferred and gathered from: Chem. Eur. J. 2014, 20, 8477-8482, which is therefore incorporated herein by reference in its entirety.
The following Examples will also summarize and describe the particularly preferred synthetic steps shown in the above-illustrated Summary Diagrams 1 and 2, respectively .
Of course, those skilled in the art will encounter no difficulty, in light of the bibliographic references broadly reported herein and of their own experience in the field of organic chemical synthesis, in reproducing the same processes without having to resort to any undue additional experimentation.
Example 1
Commercial 2,6-dibromobenzaldehyde is dissolved in anhydrous CH2CI2. Propanediol, triethylorthoformate and ZrCl4 are added at room temperature and kept under agitation overnight. NaOH is then added and stirring is continued for one hour. The organic phase is separated, and the aqueous phase is extracted with Et2O. The united organic phases are washed with water and dried on MgSC4, then the volatile components are removed under a vacuum to give the acetal as a yellowish solid. Subsequently, the acetal is dissolved in THE and then n-BuLi is added at -78°C for 25 minutes, followed by other 90 minutes of agitation at the same temperature. The reaction mixture is then treated with methyl iodide and stirred for 25 minutes at -78°C. The reaction mixture is then left to heat to room temperature for about 1.5 hours. The resulting solution is quenched with HCl and stirred at room temperature for 1.5 hours.
The complete deprotection of the aldehyde is verified by gas chromatography (GC) analysis.
The reaction mixture is subsequently extracted with Et2O, the united organic layers are washed with a solution of 10% aqueous sodium thiosulfate and water, dried on MgSO4, filtered and evaporated under a vacuum. The resulting yellowish solid is purified by distillation in a Kugelrohr apparatus to give the final product as white crystals.
The modes of operation and the reagent quantities employed were inferred and gathered from: Krzeszewski, M; et al., Chemistry-A European Journal 2016, 22(46), 16478, which is therefore incorporated herein by reference in its entirety.
Example 2
2 ,6-Dibromobenzaldehyde, phenylboronic acid, K2CO3 and Pd(OAc)2 are introduced into a Schlenk flask, and all is purged with argon before use.
A toluene/water mixture (1:1, v:v) is added into the flask, and the resulting mixture is stirred at 80°C for 16 hours. After cooling, the two phases are separated and the aqueous phase is extracted with ethyl acetate. The organic phases are combined and the solvent is evaporated. The raw product thus obtained is then purified by flash chromatography through silica gel.
The modes of operation and the reagent quantities employed were inferred and gathered from: Krzeszewski, M; et al., Chemistry-A European Journal 2016, 22(46), 16478, which is therefore incorporated herein by reference in its entirety.
Example 3
63%
2,6-Dibromobenzaldehyde, 2- (tributylstannyl)thiophene and [Pd(PPh3)4] are introduced into a Schlenk flask, and all is purged with argon before use.
Toluene is added into the flask, and the resulting mixture is stirred for additional 15 minutes. Then the two phases are separated and the aqueous phase is extracted with ethyl acetate. The organic phases are combined and dried, and then the solvent is evaporated. The raw product thus obtained is purified by flash chromatography through silica gel.
The modes of operation and the reagent quantities employed were inferred and gathered from: Krzeszewski, M; et al., Chemistry-A European Journal 2016, 22(46), 16478, which is therefore incorporated herein by reference in its entirety.
Example 4
Dibromobenzaldehyde, benzo [b]thien-3-yl-boronic acid, K2CO3, PPh3 and Pd(OAc)2 are introduced into a Schlenk flask, and all is purged with argon before use. A mixture of toluene/water (1:1, v:v) is added into the flask, and the resulting mixture is stirred for 16 hours at 80°C. After cooling, the two phases are separated and the aqueous phase is extracted with ethyl acetate.
Then the organic phases are combined and dried, and the solvent is evaporated. The raw product thus obtained is purified by flash chromatography through silica gel.
The modes of operation and the reagent quantities employed were inferred and gathered from: Krzeszewski, M; et al., Chemistry-A European Journal 2016, 22(46), 16478, which is therefore incorporated herein by reference in its entirety.
Example 5
O
96%
2-Bromobenzaldehyde, PdCl2 and CuI are dissolved in a mixture of triethylamine and anhydrous THE, then the desired corresponding alkyne is added and the reaction is stirred by reflux for 3 hours. The reaction mixture is then cooled, filtered through a layer of celite/silica gel using Et2O as a solvent. The organic fraction is concentrated under reduced pressure, and a chromatography of the residue through a column of silica gel gives the above purified final product 3. The modes of operation and the reagent quantities employed were inferred and gathered from: Kaiser, Reinhard P.; et al., Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in its entirety.
Example 6
A solution of 2-ethynylbenzaldehyde in THE is added by syringe to a mixture of 2-bromobenzaldehyde, Pd (PPh3)2C12, CuI and Et3N in anhydrous THE at room temperature under hydrogen atmosphere. The reaction mixture is heated to 80°C under agitation for 1.5 hours. The reaction mixture is filtered and the precipitate is washed with water. The filtrate is then concentrated under reduced pressure, and the residue thus obtained is purified by chromatography through a column of silica gel to give the above compound 3.
The modes of operation and the reagent quantities employed were inferred and gathered from: Sota, Yumi; et al., Chemistry-A European Journal 2015, 21(11), 4398, which is therefore incorporated herein by reference in its entirety.
Example 7
The starting compound, CuI and Et3N are added to a mixture of dichlorobis (triphenylphosphine)palladium and aryl halide in THE. The resulting mixture is stirred at 50°C overnight, then the reaction mixture is diluted with a saturated aqueous solution of NH4CI. The resulting mixture is extracted three times with ethyl acetate, then the organic extracts are combined, washed with brine and dried on Na2SO4. The mixture is filtered and evaporated under reduced pressure. Finally, the residue is purified by chromatography through silica gel to give the above final product 3.
The modes of operation and the reagent quantities employed were inferred and gathered from: Yoshida, Kazuhiro; et al., Chemistry-A European Journal 2011, 17(1), 344, which is therefore incorporated herein by reference in its entirety.
Example 8
Trimethylsilylacetylene, CuI and Et3N are added to a mixture of dichlorobis (triphenylphosphine)palladium and aryl halide in THE. The resulting mixture is kept under agitation at 50°C overnight, then the reaction mixture is diluted with a saturated aqueous solution of NH4CI. The resulting mixture is extracted three times with ethyl acetate, then the organic extracts are
combined, washed with brine and dried on Na2SO4. The mixture is filtered and evaporated under reduced pressure. Finally, the residue is purified by chromatography through silica gel to give the product. K2CO3 is added to acetylene protected with trimethylsilyl. The mixture is diluted with water and then extracted three times with CH2CI2. The organic layers are then united, washed with brine and dried on Na2SO4. The mixture is filtered and evaporated under reduced pressure, and the residue is purified by chromatography through a column of silica gel to give the product. The latter, CuI and Et3N are added to a mixture of dichlorobis (triphenylphosphine)palladium and aryl halide in THF. The resulting mixture is kept under agitation at 50°C overnight, then the reaction mixture is diluted with a saturated aqueous solution of NH4CI. The resulting mixture is extracted three times with ethyl acetate, then the organic extracts are combined, washed with brine and dried on Na2SO4. The mixture is filtered and evaporated under reduced pressure. Finally, the residue is purified by chromatography through silica gel to give the above final product 3.
The modes of operation and the reagent quantities employed were inferred and gathered from: Yoshida, Kazuhiro; et al., Chemistry-A European Journal 2011, 17(1), 344, which is therefore incorporated herein by reference in its entirety.
Example 9
2-Bromobenzaldehyde, PdCl2(PPh3)2 and CuI are dissolved in a mixture of triethylamine and anhydrous THE, then the corresponding alkyne is added and the reaction is stirred by reflux for 3 hours. Subsequently, the reaction mixture is cooled and filtered through a layer of celite/silica gel using Et2O as a solvent. The organic fraction is concentrated under reduced pressure and then a chromatography through a column of silica gel of the residue gives the above final product 3.
The modes of operation and the reagent quantities employed were inferred and gathered from: Angew. Chem. Int. Ed. 2019, 58, 17169-17174, which is therefore incorporated herein by reference in its entirety.
Example 10
Cyanideion(2moles), hydrogencyanideor alkylsilylcyanide/deprotection
Theseintermediateproductsarenovel,sincetheydonotexistintheliterature
This type of reaction is a reaction of addition of 2 moles of cyanide ion, hydrogen cyanide or alkylsilyl cyanide (with subsequent deprotection) to the aldehyde. The reaction is novel, but the reaction type is
classical and generally feasible. To the inventor's knowledge, the intermediate product 5b (cyanohydrin or cyanohydrin silyl ether) is not known in the literature; therefore, it is a part of the present invention.
There are many scientific publications about the reaction of addition of cyanide ion, hydrogen cyanide or cyanohydrin silyl ether to the aldehyde. The following may be mentioned as non-limiting examples: a)
Bandgar, B.P., et al., Green Chemistry 2001, 3(5), 265; or b)
Yoneda, R., et al., Chem. Pharm. Bull. 1987, 35(9), 3850; or, as an alternative, the general procedure for the alkynylation reaction may be followed, which uses the same reagent (2,2'-ethyne-1,2-diyl)dibenzaldehyde and/or derivatives thereof), as described in Kaiser,
R.P., et al., Angew. Chem. Int Ed. 2019, 58, 17169,
but, instead of the alkyne, in the present invention 2 cyanide ions, hydrogen cyanide or cyanohydrin silyl ether are used to give the cyanohydrin of the 5b type of the invention.
The modes of operation and the reagent quantities employed for this reaction were inferred and gathered from the aforementioned Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in its entirety.
This reaction is then followed by the cocyclotrimerization reaction previously described herein, to give the pyridazinic compound 6b.
Example 11
To the inventor's knowledge, the starting compound (6b) and the oxidized product obtained therefrom are not known in the scientific literature; therefore, they are also a part of the present invention.
Many scientific publications exist about the oxidation reaction, but the most interesting and preferable one for the purposes of the present invention is described in Angew. Chem. Int. Ed. 2019, 58, 17169, wherein:
PCC (Precipitated Calcium Carbonate) and celite are added to a solution of the diol in anhydrous CH2CI2 under argon atmosphere, and the resulting mixture is stirred for 3 hours at 25°C. Subsequently, the reaction mixture is filtered through a layer of silica gel/celite, washed with CH2CI2 and concentrated under reduced pressure. A chromatography through a column of silica gel gives the desired oxidized product.
The modes of operation and the reagent quantities employed for the oxidation reaction of the present example were inferred and gathered from the aforementioned Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in its entirety.
Example 12
A solution of 2-bromobiphenyl in anhydrous THE is
cooled to -78°C and n-BuLi is added dropwise thereto. The resulting solution is stirred for 30 minutes, followed by the addition of the starting product in THF, and initially kept under agitation at -78°C, but subsequently allowed to reach room temperature. The reaction mixture is then poured in a saturated aqueous solution of NaHCO3 and extracted with Et2O. The organic fractions are united, dried on MgSO4 filtered and concentrated under reduced pressure, and then the excess 2-bromobiphenyl is removed by chromatography through silica gel. The raw product is dissolved in CH3COOH and HC1, and the resulting solution is stirred by reflux for 2 hours. The reaction mixture is subsequently diluted with water and neutralized with a saturated solution of K2CO3, then extracted with Et2O. The organic fractions are united, dried on MgSO4, filtered and concentrated under reduced pressure. A chromatography through a column of silica gel gives the desired final product B).
The modes of operation and the reagent quantities employed for this reaction were inferred and gathered from the aforementioned Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in its entirety.
Example 13
To the inventor's knowledge, the intermediate product 4 is not known in the scientific literature; therefore, it is also a part of the invention. n-BuLi is added dropwise to a solution of alkyne in anhydrous THE at -78°C. After stirring, the starting compound in THE is added and the reaction mixture is first stirred at -78°C and then allowed to heat to room temperature, still under agitation. Subsequently, an aqueous solution of NH4CI is used in order to quench the reaction mixture, which is then extracted with Et2O. The organic fractions are united, washed with a saturated solution of NaCl, separated and dried on Na2SO4, filtered and concentrated under reduced pressure. A chromatography through a column of silica gel of the obtained residue gives the desired product 4.
The modes of operation and the reagent quantities employed for this alkynylation reaction were inferred and gathered from the aforementioned Angew. Chem. Int. Ed. 2019, 58, 17169, which, among the numerous scientific publications on this topic, turned out to be the most suitable for the purposes of the present invention, and is therefore incorporated herein by reference in its entirety.
Example 14
To the inventor's knowledge, the starting compound 4 and the intermediate 5a are not known in the scientific literature; therefore, they are also a part of the invention.
As previously described, this type of reaction is a reaction of addition of a cyanide ion, hydrogen cyanide or alkylsilyl cyanide (with subsequent deprotection) to the aldehyde. Among the many scientific publications about the reaction of addition of cyanide ion, hydrogen cyanide or cyanohydrin silyl ether to the aldehyde, a particularly preferred one for the purposes of the present invention turned out to be Kaiser, Reinhard P.; et al., Angew. Chem. Int. Ed. 2019, 58, 17169. The modes of operation and the reagent quantities employed for this reaction were, in fact, inferred and gathered from the same publication, which is therefore incorporated herein by reference in its entirety.
This reaction is then followed by the above-described cocyclotrimerization reaction to give the pyridinic compound 6a.
Example 15
To the inventor's knowledge, the starting compound 6a and the corresponding oxidized intermediate thus obtained are not known in the scientific literature;
therefore, they are also a part of the invention.
The two reactions of this example, wherein the pyridinic derivative A of Summary Diagram 1 is formed, are similar to those previously described for the preparation of the pyridazinic compound B of Summary Diagram 1 in Examples 11 and 12, and are executed in the same way. In this case as well, the modes of operation and the reagent quantities employed for these reactions were inferred and gathered from the aforementioned Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in its entirety.
Example 16
The phenyl derivative of 2-bromobenzaldehyde (the above-described compound 7 of Summary Diagram 2), PdCl2(PPh3)2 and CuI are dissolved in a mixture of Et3 and anhydrous THE, then the corresponding alkyne is
added and the reaction is stirred by reflux for 3 hours. The reaction is then cooled and filtered through a layer of celite/silica gel using Et2O as a solvent. The organic fraction is then concentrated under reduced pressure and the residue is purified by chromatography through silica gel to give the product 8.
The modes of operation and the reagent quantities employed for this reaction were inferred and gathered from Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in its entirety.
Example 17
To the inventor's knowledge, the intermediate product 10b (cyanohydrin, but also cyanohydrin silyl ether) is not described in the scientific literature; therefore, it is a part of the invention.
This reaction is a reaction of nucleophilic addition of 2 moles of cyanide ions, hydrogen cyanide or alkyl silyl cyanide (with subsequent deprotection) which is similar to those previously described herein, and is therefore carried out, for example, in the same conditions and with substantially the same quantities as in the similar reaction previously described in Example 10.
This reaction is then followed by the above-described
cocyclotrimerization reaction to give the pyridazinic compound lib.
EXAMPLE 18
To the inventor's knowledge, the starting compound lib and the corresponding oxidized intermediate thus obtained are not known in the scientific literature; therefore they are also a part of the invention.
The two reactions of this Example, wherein the pyridazinic derivative B') of Summary Diagram 2 is formed, are similar to those previously described for the preparation of the pyridazinic derivative B) of Summary Diagram 1 in Examples 11 and 12, and are executed in the same way. In this case as well, the modes of operation and the reagent quantities employed for these reactions were inferred and gathered from the aforementioned Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in
its entirety.
Example 19
To the inventor's knowledge, the intermediate product 9 is not described in the scientific literature; therefore, it is a part of the invention. n-BuLi is added dropwise to a solution of alkyne in anhydrous THE at -78°C, and the reaction is first stirred at -78°C and then left to heat to room temperature, still under agitation. The reaction mixture is then quenched by adding an aqueous solution of NH4CI and extracted with Et2O, and the organic phases are united, washed with a saturated solution of NaCl, dried on anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue thus obtained is purified by chromatography through a column of silica gel to give the above intermediate product 9.
The modes of operation and the reagent quantities employed for this alkynylation reaction were inferred and gathered from the aforementioned Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in its entirety.
Example 20
To the inventor's knowledge, the starting product 9 and the intermediate product 10a are not described in the scientific literature; therefore, they are also a part of the invention.
This reaction is a reaction of nucleophilic addition of a cyanide ion, hydrogen cyanide or alkylsilyl cyanide (with subsequent deprotection) to the aldehyde which is similar to the one previously described herein, and is therefore carried out, for example, in the same conditions and with substantially the same quantities as in the similar reaction described in Example 14.
This reaction is likewise followed by the above-described cocyclotrimerization reaction to give the pyridinic compound 11a.
Example 21
To the inventor's knowledge, the starting compound 11a and the oxidized intermediate product are not known in the scientific literature; therefore, they are also a part of the invention.
The two reactions of this Example, wherein the pyridinic derivative A') of Summary Diagram 2 is formed, are similar to those previously described for the preparation of the pyridinic derivative A) of Summary Diagram 1 in Example 15, and are executed in the same way. In this case as well, the modes of operation and the reagent quantities employed for these reactions were inferred and gathered from the aforementioned Angew. Chem. Int. Ed. 2019, 58, 17169, which is therefore incorporated herein by reference in its entirety.
Example 22
Suzuki reaction
The Suzuki reaction, previously mentioned in Summary Diagram 1, is a cross-coupling reaction where the coupling partners are a boronic acid and an organohalide catalyzed by a Pd(0) complex. It was first published in 1979 by Akira Suzuki (Miyaura, N.; Yamada, K.; Suzuki, A.; et al.; Tetrahedron Lett. 1979, 36,
3437).
In this type of reaction, a carbon-carbon single bond is formed by coupling an organoboron species with a halide using a palladium catalyst and a base.
The Suzuki coupling is effected via three key steps:
- Oxidative Addition,
- Transmetalation,
- Reductive Elimination.
Through this type of reaction it is possible to obtain the above-described compounds 2 of Summary Diagram 1.
Example 23
Sonogashira reaction
The Sonogashira reaction (Sonogashira, K.; Tohda, Y.;
Hagihara, N.; Tetrahedron Lett. 1975, 50, 4467), previously mentioned in Summary Diagram 1 and Summary Diagram 2, is a cross-coupling reaction where the
coupling partners are a terminal alkyne and an aryl- or vinyl- halide. It uses a Pd(0) catalyst and a Cu (I) cocatalyst to form a carbon-carbon single bond.
The Sonogashiara coupling is effected via four key steps:
- Oxidative Addition,
- Transmetalation,
- trans/cis Isomerization,
- Reductive Elimination.
Through this type of reaction it is possible to obtain the above-described compounds 3 of Summary Diagram 1 and the above-described compound 8 of Summary Diagram 2.
Advantages of the Invention
Advantageously, the novel heical molecules of dispirodiindenopyridines and dispirodiindenopyridazines of the present invention have proved to have greater and better characteristics for organic electronics applications, in comparison with the other known molecules that may be taken into consideration as candidates for the same use. Said characteristics can be attributed, in particular, to the presence of: 1) largely conjugated systems, 2) chiro-optical properties due to helicity, 3) spiro residues (which confer increased morphologic stability, while at the same time maintaining the electronic properties and having higher solubility than the corresponding compounds without spiro groups), 4) increased fluorescence due to the presence of the pyridazine residue and to the rigid structure of the spiro residue, and 5) functionalization due to the presence of nitrogen atoms (which may lead to formation of a so-called "push-pull" system, modulability through formation of pyridinium and pyridazinium salts, formation of N-oxides or N,N'-dioxides as anchoring groups for solar cells, and so forth).
It is also worth mentioning that dispirodiindenopyridazines seem to be the only existing class of molecules which possess two fluorophores groups (fluorene and pyridazine); thus, they permit a better modulation of optoelectronic properties such as, for example, multicolor fluorescence, and may originate new uses for making special materials such as, for example, smart luminescent materials.
Being spiro compounds, dispirodiindenopyridines and
dispirodiindenopyridazines are characterized by steric factors that prevent solid-state packing; as a consequence, they have proved to be capable of reducing intermolecular interaction, thereby preserving the color purity and spectral stability of the fluorescence.
Moreover, due to the presence of spiro residues, they have an interesting potential for use as active materials for OLEDs, OTFTs, photodetectors, solar cells or lasers.
The chiro-optical properties of the helical dispirodiindenopyridines and dispirodiindenopyridazines are important in organic electronics, e.g. for the electronic circular dichroism or for use in chiral sensors. In fact, chirality is an additional property which is advantageous for organic electronics.
The protonation of the nitrogen atom may originate multicolor fluorescence because of the emission variation; this is essential for a smart luminescent material.
Furthermore, the presence of the nitrogen atom permits the functionalization and formation of a system characterized by the presence of a donor and an acceptor of electrons; all this is fundamental for the polarization of a "push-pull" system.
In addition, the formation of N-oxide turned out to be essential to confer the organic sensitizer property on the anchoring in a solar cell in order to increase absorption, i.e. to attain higher energy conversion efficiency.
The study of the present invention on the preparation
of the novel classes of molecules, i.e. dispirodiindenopyridines and dispirodiindenopyridazines, and on their potential uses started from a preliminary study on candidate organic molecules for use in electronics: spiro compounds, helicenes and dispiroindenofluorenes.
Although efficient, such molecules have a limited number of properties useful for organic electronics in comparison with the dispirodiindenopyridines and dispirodiindenopyridazines of the present invention. Today, the technologies based on crystalline silicon are dominating the production of photovoltaic panels. Crystalline silicon offers many advantages, such as abundance, a radicated basic technology, the fact that it is a high-quality, high-stability material. Nevertheless, the most important drawbacks connected with silicon use are its indirect energy gap and the high costs incurred for fabricating silicon-based materials and devices.
In turn, the most interesting aspect of organic cells is the use of the potentials of the thin-film technology: the very small thicknesses, of the order of a few millionths of a millimeter, permit the realization of panels on flexible and light plastic substrates. In addition to lightness and flexibility characteristics, organic cells have the advantage that they can have different hues. The derivative compounds of dispirodiindenopyridines and dispirodiindenopyridazines of the present invention have thus proven to be particularly promising and useful for use in the organic electronics field.
Industrial Applicability
The present invention has made it possible to realize novel derivative heical molecules of dispirodiindenopyridines and dispirodiindenopyridazines , and derivatives thereof, which have proven to be particularly useful in organic electronics applications, in comparison with both the inorganic compounds currently in use and the other organic molecules currently being taken into account as possible competitive candidates for such applications.
List of the most important commercially available compounds
2.6-dibromo-4-methylbenzaldehyde (Aldrich Partners Product-USA, AK Scientific Product Catalog, Manchester Organics Limited, AbaChemScene Product List, etc.)
2.6-dibromo-4-ethylbenzaldehyde (FCH Group Reagents for Synthesis, Aurora Building Blocks 5 and HE Chemical Product List)
3.5-dibromo- [1,1'-biphenyl]-4-carbaldehyde (Chemieliva Pharmaceutical Product List and Hong Kong Chemhere Co., Ltd)
2.6-dibromo-4-methoxybenzaldehyde (Aldrich Partners Product-USA, BIONET Screening and Fragments Library, BIONET Research Intermediates, FCH Group Reagents for Synthesis, etc.)
2.6-dibromo-4-ethoxybenzaldehyde (FCH Group Reagents for Synthesis, Aurora Building Blocks 8 and HE Chemical Product List)
2.6-dibromo-3-methoxybenzaldehyde (AOBChem USA
Product List, FCH Group Reagents for Synthesis, Aurora
Building Blocks 5, HE Chemical Product List, etc.)
2,6-dibromobenzaldehyde (Aldrich Partners Product- USA, TCI America Research Chemicals, TCI Europe Research Chemicals, TCI UK Research Chemicals, etc.)
2-bromobenzaldehyde (TCI America Research Chemicals, TCI Europe Research Chemicals, TCI UK Research Chemicals, BIONET Screening and Fragments Library)
3-dibromo-[1,1'-biphenyl]-2-carbaldehyde
(Chemieliva Pharmaceutical Product List)
2-bromo-4-methoxybenzaldehyde (Aldrich Partners Product-USA, Accela ChemBio Product List, BIONET Research Intermediates, Synthonix Product List, etc.)
2-bromo-4-trifluoromethylbenzaldehyde (Aldrich Partners Product-USA, BIONET Research Intermediates, Synthonix Product List, ALDRICH, etc.)
2-ethynylbenzaldehyde (BIONET Screening and Fragments Library, Accela ChemBio Product List, BIONET Research Intermediates, Synthonix Product List, etc.)
1-bromo-2-naphthaldehyde (TCI America Research Chemicals, TCI Europe Research Chemicals, TCI UK Research Chemicals, TCI Shanghai Research Chemicals, etc.)
2-bromo-6-methylbenzaldehyde (Aldrich Partners Product-USA, BIONET Research Intermediates, Synthonix Product List, ALDRICH, etc.)
2,2'-(ethyne-1,2-diyl)dibenzaldehyde (Aurora Building Blocks 7)
List of Quoted References
Angew. Chem. Int. Ed. 2019, 58, 17169-17174
Chem. Eur. J. 2014, 20, 8477-8482
Org. Lett., Vol.9, No.3, 2007
Krzeszewski, M; et al., Chemistry-A European Journal 2016, 22(46), 16478
Sota, Yumi; et al., Chemistry-A European Journal 2015, 21(11), 4398
Yoshida, Kazuhiro; et al., Chemistry-A European Journal 2011, 17(1), 344
Ryuj1 Yoneda, Hideki Hisakawa, Shinya Harusawa, and Takushi Kurihara; Chem. Pharm. Bull. 1987, 35(9), 3850 B. P. Bandgar and V. T. Kamble; Green Chemistry 2011, 3, 265 Gennaro Pescitelli, Lorenzo Di Bari and Nina Berova; Chem. Soo. Rev. 2011, 40, 4603 Christopher A. Fleckenstein and Herbert Plenio; Chem. Eur. J. 2007, 13, 2701 Mengwei Li, Yuan, and Yulan Chen; ACS Appl. Mater. Interfaces 2018, 10, 1237 Beverly J. Cohen, Hiroaki Baba, and Lionel Goodman; J. Chem. Phys. 1965, 43, 2902 Hong-Tai Chang, Masilamani Jeganmohan, and Chien-Hong Cheng; Organic Letters 2007, Vol. 9, No. 3, 505 Filip Bures; RSC Adv. 2014, 4, 58826
Lei Wang, Xichuan Yang, Shifeng Li, Ming Cheng and Licheng Sun; RSC Advances 2013, 3, 13677 Wenbo Chen, Souad A. Elfeky, Yse Nonne, Louise Male, Kabir Ahmed, Claire Amiable, Philip Axe, Shinji Yamada, Tony D. James, Steven D. Bull and John S. Fossey; Chem. Commun. 2011, 47, 253 Tobat P. I. Saragi, Till Spehr, Achim Siebert, Thomas Fuhrmann-Lieker and Josef Salbeck; Chem. Rev. 2007,
107, 1011
Kenkichi Sonogashira, Yasuo Tohda, and Nobue Hagihara;
Tetrahedron Letters 1975, No.50, 4467
Norio Miyaura, Kinji Yamada, and Akira Suzuki;
Tetrahedron Letters 1979, No.36, 3437
Claims
1. Derivative compounds of helical dispiroindenopyridines and/or dispiroindenopyridazines of general formula A) and/or A') and/or B) and/or B'), respectively:
wherein R and R' independently represent hydrogen; a straight-chain or branched-chain C1-C6 hydrocarbon group such as, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, neo-pentyl, hexyl, optionally substituted, for example, with hydroxyl, alcoxyl, ether, ester, halogen, amine; an aromatic group, optionally substituted, for example, with phenyl, benzyl, p-tolyl, 4-methoxyphenyl, 4- bromophenyl, (trifluoromethyl) benzyl, thiophen-3-yl, naphthalen-l-yl, o-tolyl, wherein, however, branched alkyl substituents or aromatic ones are preferred in order to stiffen the structure so as to promote fluorescence; or a trimethylsilyl group; the X's
represent each, independently, a straight-chain or branched-chain C1-C6 hydrocarbon group, such as, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, neo-pentyl, hexyl, optionally substituted, for example, with hydroxyl, alcoxyl, ether, ester, halogen, amine, wherein, however, those substituents which facilitate electronic delocalization for fluorescence are preferred; a trifluoromethyl group; a difluoromethyl group; a phenyl group; a benzyl group; or an alcoxyl group.
2. A method for the preparation of a compound of general formula A) and/or B) according to claim 1, as described in Summary Diagram 1 in the above description.
3. A method for the preparation of a compound of general formula A') and/or B') according to claim 1, as described in Summary Diagram 2 in the above description.
4. Use of at least one compound of general formula A) and/or A') and/or B) and/or B') according to claim 1 for applications in the field of organic electronics.
5. A composition and/or a device comprising at least one of the compounds of general formula A) and/or A') and/or B) and/or B') according to claim 1, for use, in accordance with claim 4, in the field of organic electronics.
6. The compound of formula 5b, highlighted in Summary Diagram 1, as an intermediate for the preparation of the compound 6b.
7. The oxidized compound obtained by oxidation of the compound 6b of claim 6, described in Summary Diagram 1 and Example 11, as an intermediate for the preparation of the final compound B).
8. The compound of formula 4 highlighted in Summary Diagram 1, as an intermediate for the preparation of the compound 5a.
9. The compound of formula 5a highlighted in Summary Diagram 1, as an intermediate for the preparation of the compound 6a.
10. The oxidized compound obtained by oxidation of the compound 6a of claim 9, described in Summary Diagram 1 and Example 15, as an intermediate for the preparation of the final compound A).
11. The compound of formula 10b highlighted in Summary Diagram 2, as an intermediate for the preparation of the compound lib.
12. The compound of formula lib highlighted in Summary Diagram 2, as an intermediate for the preparation of the corresponding oxidized compound, described in Summary Diagram 2 and Example 18.
13. The oxidized compound obtained by oxidation of the
compound lib of claim 12, described in Summary Diagram 2 and Example 18, as an intermediate for the preparation of the final compound B').
14. The compound of formula 9 highlighted in Summary Diagram 2, as an intermediate for the preparation of the compound 10a.
15. The compound of formula 10a highlighted in Summary Diagram 2, as an intermediate for the preparation of the compound 11a.
16. The compound of formula 11a highlighted in Summary Diagram 2, as an intermediate for the preparation of the final compound A').
17. Plastic substrate or the like for screens, displays or other electronic components or apparatuses, comprising a fluorescent film comprising helical molecules derived from dispirodiindenopyridines and dispirodiindenopyridazines, and derivatives thereof.
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